含腺嘌呤聚芳醚砜质子交换膜的制备与性能研究

发布时间：2018-03-19 12:28

本文选题：燃料电池　切入点：质子交换膜　出处：《兰州大学》2017年硕士论文　论文类型：学位论文

【摘要】：质子交换膜作为质子交换膜燃料电池的核心组成部分,直接决定着燃料电池工作性能与使用寿命,目前由杜邦公司生产并制造的商业化Nafion系列膜具有较高的质子传导率以及良好的综合性能,但以Nafion膜为代表的全氟磺酸型质子交换膜依旧存在诸如甲醇渗透率高、造价昂贵、易溶胀、质子传导率严重依赖膜内含水量等缺点。虽然以改性、掺杂、交联等方法为基础的磺化芳香族聚合物使磺酸型质子交换膜的性能得到了一定改善,但高磺化度的磺化芳香族聚合物仍然会使膜过度溶胀,降低水和条件下的稳定性。酸碱类聚合物质子交换膜通过聚合物结构中带有碱性的官能团与掺杂的酸性基团进行酸碱相互作用,或者以聚合物中同时存在的酸性与碱性基团进行作用,使聚合物膜吸收一定含量的酸来完成质子传导。这类质子交换膜对湿度的依赖较低,具有较为可观的质子传导能力,而且在热稳定性、吸水溶胀率以及耐水解性等综合性能方面都能够满足质子交换膜的要求。本文选取具有较好的机械性能、优异的热稳定性以及耐腐蚀性能的聚芳醚砜为主体材料,以具有碱性基团且能以氢键作用进行结合的生命体重要组成结构——碱基腺嘌呤为改性结构,设计并制备溶胀率较低、传导率较高、综合性能良好的酸碱性质子交换膜,主要从以下两方面进行研究。具体包括:1.通过接枝的方法将腺嘌呤接入到聚合物侧链,制备侧链含有腺嘌呤结构的聚芳醚砜类聚合物,通过聚芳醚砜侧链的碱性基团与掺杂盐酸进行作用,形成腺嘌呤接枝型酸碱质子交换膜PAES-A-x,同时测试了PAES-A-x的质子传导率以及其他综合性能。结果表明,腺嘌呤接枝型酸碱质子交换膜PAES-A-x具有较为可观的质子传导率,且在具有较低溶胀率的同时,具有良好的热稳定性和机械性能以满足质子交换膜材料的要求。2.制备主链含有带吡啶结构的Cardo型聚芳醚砜材料,进一步掺杂碱基腺嘌呤与聚合物通过氢键作用进行结合,掺杂盐酸后,形成酸化的PPAES/A-x复合质子交换膜,测试该掺杂型质子交换膜PPAES/A-x的各项性能,并阐述腺嘌呤引入下碱性基团和盐酸作用后对于质子传导率以及其他综合性能的影响。结果表明,分子间氢键作用下的PPAES/A-x膜具有良好的吸水率与传导率的同时,显著降低了溶胀率,其热稳定性和氧化稳定性等其他综合性能均表现出较高水平。
[Abstract]:The core of the proton exchange membrane as proton exchange membrane fuel cell component, directly determines the performance of the fuel cell and the service life of the proton conduction at present by commercial film DuPont Co Nafion series production and manufacturing has high efficiency and good overall performance, but the fluorosulfonic proton membrane with Nafion as the representative of the exchange film still problems such as high cost, high methanol permeability, easy to swelling, proton conductivity is heavily dependent on membrane water content and other disadvantages. Although the modification, doping, sulfonated aromatic polymer crosslinking method based sulfonic acid proton exchange membrane performance that has been some improvement, but the sulfonated aromatic polymer with high sulfonation degree will still the film excessive swelling, reduce water and stability. Under the condition of functional groups and polymers doped with acid-base proton exchange membrane by polymer structure with alkaline acid Groups of acid-base interactions, or acidic and basic groups also exist in the polymer, the polymer film absorption of certain content of acid to complete proton transfer. This type of proton exchange membrane depends on the humidity is low, with considerable proton conduction ability, and the thermal stability, swelling rate and hydrolysis and other aspects of the comprehensive performance can meet the requirements of the proton exchange membrane. This paper has good mechanical properties, excellent thermal stability and corrosion resistance of polyarylethersulfone as main material, with alkali group and in hydrogen bonding with the weight of life structure is composed of modified adenine the structure, design and preparation of the swelling rate is low, high conductivity, good comprehensive properties of acid-base proton exchange membrane, mainly from the following two aspects including: 1.. The method will be access to the adenine graft polymer side chain, preparation of side chain containing adenine structure poly aryl ether sulfone polymers, the poly aryl ether sulfone side chain alkaline groups and doping hydrochloric acid, the formation of adenine grafted acid-base proton exchange membrane PAES-A-x, and tested the proton conductivity of PAES-A-x and the other comprehensive performance. The results showed that the graft type acid-base proton exchange membrane adenine PAES-A-x has considerable proton conduction rate, and has low swelling rate and has good thermal stability and mechanical properties to meet the requirements of the.2. proton exchange membrane material prepared with pyridine containing Cardo type main chain structure of polyarylethersulfone materials further, doped with adenine and polymer are combined through hydrogen bonding, doped with hydrochloric acid after the formation of the PPAES/A-x composite proton exchange membrane to test the acidification, doped proton exchange The properties of PPAES/A-x film, and expounds the influence on the proton conductivity and other properties of the adenine introduced basic groups and hydrochloric acid. The results show that the intermolecular hydrogen bonding interactions under the PPAES/A-x membrane has good water absorption rate and the transmission rate at the same time, significantly reduced the swelling ratio, its thermal stability and oxidation stability etc. other properties are exhibited a higher level.

【学位授予单位】：兰州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TM911.4;TB383.2

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